3-(β-aminoethyl)-4-cyano-isothiazolylazo dyes

ABSTRACT

A compound of the formula: ##STR1## where R is hydrogen, C 1  -C 4  -alkyl, phenyl, chlorophenyl, methylphenyl, methoxyphenyl or nitrophenyl; R 1  is allyl, C 1  -C 8  -alkyl, C 1  -C 8  -alkyl substituted by C 1  -C 8  -alkoxy, phenoxy, phenyl or C 1  -C 8  -alkanoyloxy, cyclopentyl, cyclohexyl, methylcyclohexyl, norbornyl, phenyl or phenyl substituted by chlorine, methyl or alkoxy; R 2  is C 1  -C 10  -alkanoyl, C 1  -C 10  -alkanoyl substituted by alkoxy or phenoxy, cyclohexanoyl, benzoyl, benzoyl substituted by chlorine, methyl or methoxy, C 1  -C 8  -alkoxycarbonyl, aminocarbonyl, phenylaminocarbonyl, CH 3  NHCO, C 2  H 5  NHCO, C 3  H 7  NHCO, C 4  H 9  NHCO, (CH 3 ) 2  NCO, CH 3  SO 2 , C 6  H 5  SO 2  or p--CH 3  --C 6  H 4  --SO 2  ; or R 1  and R 2 , together with the nitrogen atom, form a ring system, and K is a radical of a coupling component. The isothiazolylylazo compound of the invention is useful for the dyeing of the polyesters, nylon, and cellulose esters.

The present invention relates to compounds of the general formula I ##STR2## where R is hydrogen, C₁ -C₄ -alkyl or unsubstituted or substituted phenyl, R¹ is allyl, unsubstituted or substituted alkyl, cycloalkyl or aryl, R² is acyl, R¹ and R², together with the nitrogen, form a saturated 5-membered or 6-membered ring or a diacylimide radical, and K is a radical of a coupling component.

Specific examples of radicals R, in addition to hydrogen, are butyl, propyl, ethyl, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, nitrophenyl and, preferably, methyl.

Examples of suitable radicals R¹ are C₁ -C₈ -alkyl which may furthermore be interrupted by oxygen and substituted by C₁ -C₈ -alkoxy, phenoxy, phenyl or C₁ -C₈ -alkanoyloxy, and cyclopentyl, cyclohexyl, methylcyclohexyl and norbornyl, and phenyl which is unsubstituted or substituted by chlorine, methyl or alkoxy.

Specific examples of radicals R¹ in addition to those stated above are: CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₁₃, C₈ H₁₇, C₂ H₅ OCH₂ CH₂, CH₃ OCH₂ CH₂ CH₂, C₄ H₉ OCH₂ CH₂ CH₂, CH₃ CONHCH₂ CH₂, C₂ H₅ OCOCH₂, CH₃ OCOCHCH₃, C₆ H₅ OCH₂ CH₂, C₆ H₅ OCH₂ CH₂ OCH₂ CH₂ CH₂, C₆ H₅ CH₂, C₆ H₅ CH₂ CH₂, ##STR3##

In the case of radicals which can occur in isomeric form, the n-, iso- and tert.-compounds are all embraced by the abbreviated formula.

R² is, for example, C₁ -C₁₀ -alkanoyl which may furthermore be substituted by alkoxy or phenoxy, or is cyclohexanoyl, or is benzoyl which is unsubstituted or substituted by chlorine, methyl or methoxy, or is C₁ -C₈ -alkoxycarbonyl, unsubstituted, N-monosubstituted or N,N-disubstituted aminocarbonyl or phenylaminocarbonyl or the corresponding alkyl-, aryl- or aminosulfonyl radicals.

Specific examples of acyl radicals R₂ are CHO, ##STR4##

R¹ and R² together with the nitrogen form, for example, the following radicals: ##STR5##

The coupling components KH are derived from, in particular, the aniline, naphthalene or heterocyclic series.

The coupling components KH are of, in particular, the general formulae ##STR6## where R³ is hydrogen, alkyl, aralkyl or aryl, R⁴ is hydrogen or R⁵, R⁵ is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aralkyl or aryl, R⁶ and R⁷ are each hydrogen, alkyl, alkoxy, phenoxy, halogen, alkylsulfonylamino, dialkylaminosulfonylamino or acylamino, R⁸ is cyano, carbamyl, nitro or carbalkoxy and R⁹ is unsubstituted or substituted phenyl, alkyl or aralkyl.

Specific examples of radicals R³, in addition to those stated above, are methyl, ethyl, propyl, butyl, benzyl, phenethyl, phenyl, o-, m- and p-tolyl and o-, m- and p-chlorophenyl.

Examples of radicals R⁵, in addition to those stated above, are C₁ -C₆ -alkyl which can be substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyl-oxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxy-carbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexyl-aminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxy-carbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxy-carbonyl, and phenyl, benzyl, phenethyl and cyclohexyl.

Specific examples of radicals R⁵ are methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxy-butyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethyl-carbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyl-oxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxy-carbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethyl-aminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxy-carbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonyl-ethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxy-carbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxy-ethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phen-oxyethoxycarbonylethyl and 2-benzoylethyl.

Examples of suitable radicals R⁶ and R⁷ are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, C₁ -C₆ -alkanoylamino, benzylamino and C₁ -C₄ -alkylsulfonylamino and -dialkylaminosulfonylamino.

Examples of radicals R⁸ in addition to those stated above are aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- and isopropoxycarbonyl, n-, iso- and sec.-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- and isopropoxyethoxycarbonyl and n-, iso- and sec.-butoxyethoxycarbonyl.

R⁹ is, for example, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonylmethyl, cyanomethyl, benzyl or phenyl which is monosubstituted or polysubstituted by C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, phenoxy, benzyloxy, phenyl, chlorine, bromine, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -mono- or di-alkylamino, C₁ -C₄ -alkoxyethoxy, C₁ -C₄ -alkyl- or phenylmercapto or C₁ -C₅ -alkanoylamino, such as acetylamino, propionylamino, butyrylamino or valerylamino.

The compounds of the formula I have yellow to blue hues and are particularly suitable for dyeing polyesters, nylons, cellulose esters and blends of polyesters and cellulose fibers. The dyeings obtained generally have good fastness properties, particularly on polyesters.

The compounds of the formula I can be prepared by reacting a diazonium compound of an amine of the formula ##STR7## with a coupling component of the formula

    KH

by a conventional method.

The Examples which follow illustrate the preparation. Parts and percentages are by weight, unless stated otherwise.

Of particular importance are compounds of the formula Ia ##STR8## where B¹ is C₁ -C₈ -alkyl, B² is acyl and K¹ is a radical of a coupling component from the aniline or thiazole series.

Preferred coupling components K¹ H are: ##STR9##

EXAMPLE 1

11.9 parts of 5-amino-4-cyano-3-β-[N,N-acetylethylamino]-ethylisothiazole were dissolved in 75 parts by volume of a mixture of 17 parts of glacial acetic acid and 3 parts of propionic acid. 20 parts of 85% strength sulfuric acid were added, after which 16 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were run slowly into the stirred solution at 0°-5° C., and stirring was continued at the same temperature for 4 hours. The resulting diazonium salt solution was run slowly into a mixture of 12.8 parts of 4-phenyl-2-(N-diallylamino)-thiazole, 20 parts of acetic acid, 250 parts of water, 250 parts of ice and one part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried at 50° C. under reduced pressure to give 18.0 parts of the dye of the formula ##STR10## This dye dyes polyesters in deep violet hues which have good lightfastness and fastness to dry heat pleating and setting.

The dyes characterized in the Table below by diazo and coupling components are also obtained similarly to Example 1.

    __________________________________________________________________________     Ex-                                                Hue on                      ample                                                                              Diazo component           Coupling component   polyesters                  __________________________________________________________________________          ##STR11##                                                                                                ##STR12##           violet                      3    "                                                                                                        ##STR13##           violet                      4    "                                                                                                        ##STR14##           violet                      5    "                                                                                                        ##STR15##           navy                        6    "                                                                                                        ##STR16##           blue                        7    "                                                                                                        ##STR17##           blue                        8    "                                                                                                        ##STR18##           blue                        9    "                                                                                                        ##STR19##           blue                        10   "                                                                                                        ##STR20##           blue                        11                                                                                  ##STR21##                                                                                                ##STR22##           blue                        12   "                                                                                                        ##STR23##           blue                        13   "                                                                                                        ##STR24##           blue                        14   "                                                                                                        ##STR25##           blue                        15   "                                                                                                        ##STR26##           blue                        16   "                                                                                                        ##STR27##           navy                        17                                                                                  ##STR28##                                                                                                ##STR29##           violet                      18                                                                                  ##STR30##                                                                                                ##STR31##           violet                      19                                                                                  ##STR32##                 "                   violet                      20                                                                                  ##STR33##                 "                   violet                      21                                                                                  ##STR34##                                                                                                ##STR35##           navy                        22                                                                                  ##STR36##                 "                   navy                        23                                                                                  ##STR37##                 "                   navy                        24                                                                                  ##STR38##                                                                                                ##STR39##           blue                        25                                                                                  ##STR40##                 "                   blue                        26                                                                                  ##STR41##                 "                   blue                        27                                                                                  ##STR42##                                                                                                ##STR43##           blue                        28                                                                                  ##STR44##                 "                   blue                        29                                                                                  ##STR45##                 "                   blue                        30                                                                                  ##STR46##                 "                   blue                        31                                                                                  ##STR47##                 "                   blue                        32                                                                                  ##STR48##                 "                   blue                        33                                                                                  ##STR49##                 "                   blue                        __________________________________________________________________________

EXAMPLE 34

5.0 parts of 5-amino-4-cyano-3-(2'-N-ethyl- N-propionylamino)-ethylisothiazole in a mixture of 22.5 parts by volume of acetic acid and 7.5 parts by volume of propionic acid were stirred. 10 parts by volume of an 85% strength sulfuric acid were added, after which 6.4 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were run slowly into the stirred solution at 0°-5° C. and stirring was continued at the same temperature for 4 hours. The resulting diazonium salt solution was run slowly into a solution of 3.9 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 50 parts of water, 200 parts of ice, 10 parts by volume of 32% strength hydrochloric acid, 20 parts by volume of dimethylformamide and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 9.2 parts of the dye of the formula ##STR50## This dye dyes polyester fibers in clear bluish red fast hues.

The compounds below can be prepared by a similar method.

    __________________________________________________________________________                                                  Hue on                            Example                                                                             Diazo component     Coupling component  polyesters                        __________________________________________________________________________     35                                                                                   ##STR51##                                                                                          ##STR52##          red                               36                                                                                   ##STR53##                                                                                          ##STR54##          red                               37                                                                                   ##STR55##                                                                                          ##STR56##          red                               38                                                                                   ##STR57##                                                                                          ##STR58##          red                               39                                                                                   ##STR59##                                                                                          ##STR60##          red                               40                                                                                   ##STR61##                                                                                          ##STR62##          red                               41                                                                                   ##STR63##                                                                                          ##STR64##          red                               42                                                                                   ##STR65##                                                                                          ##STR66##          red                               43                                                                                   ##STR67##                                                                                          ##STR68##          red                               44                                                                                   ##STR69##                                                                                          ##STR70##          red                               45                                                                                   ##STR71##                                                                                          ##STR72##          red                               46                                                                                   ##STR73##                                                                                          ##STR74##          red                               47                                                                                   ##STR75##                                                                                          ##STR76##          red                               48                                                                                   ##STR77##                                                                                          ##STR78##          reddish violet                    49                                                                                   ##STR79##                                                                                          ##STR80##          reddish violet                    50                                                                                   ##STR81##                                                                                          ##STR82##          red                               51                                                                                   ##STR83##                                                                                          ##STR84##          red                               52                                                                                   ##STR85##                                                                                          ##STR86##          reddish violet                    53                                                                                   ##STR87##                                                                                          ##STR88##          red                               54                                                                                   ##STR89##                                                                                          ##STR90##          red                               55                                                                                   ##STR91##                                                                                          ##STR92##          red                               56                                                                                   ##STR93##                                                                                          ##STR94##          red                               57                                                                                   ##STR95##                                                                                          ##STR96##          red                               58                                                                                   ##STR97##                                                                                          ##STR98##          red                               59                                                                                   ##STR99##                                                                                          ##STR100##         reddish violet                    60                                                                                   ##STR101##                                                                                         ##STR102##         reddish violet                    61                                                                                   ##STR103##                                                                                         ##STR104##         red                               62                                                                                   ##STR105##                                                                                         ##STR106##         reddish violet                    63                                                                                   ##STR107##                                                                                         ##STR108##         red                               64                                                                                   ##STR109##                                                                                         ##STR110##         red                               65                                                                                   ##STR111##                                                                                         ##STR112##         red                               66                                                                                   ##STR113##                                                                                         ##STR114##         red                               67                                                                                   ##STR115##                                                                                         ##STR116##         red                               68                                                                                   ##STR117##                                                                                         ##STR118##         red                               69                                                                                   ##STR119##                                                                                         ##STR120##         red                               70                                                                                   ##STR121##                                                                                         ##STR122##         red                               71                                                                                   ##STR123##                                                                                         ##STR124##         red                               72                                                                                   ##STR125##                                                                                         ##STR126##         red                               73                                                                                   ##STR127##                                                                                         ##STR128##         red                               74                                                                                   ##STR129##                                                                                         ##STR130##         red                               75                                                                                   ##STR131##                                                                                         ##STR132##         red                               76                                                                                   ##STR133##                                                                                         ##STR134##         red                               77                                                                                   ##STR135##                                                                                         ##STR136##         red                               78                                                                                   ##STR137##                                                                                         ##STR138##         red                               79                                                                                   ##STR139##                                                                                         ##STR140##         red                               80                                                                                   ##STR141##                                                                                         ##STR142##         red                               81                                                                                   ##STR143##                                                                                         ##STR144##         red                               82                                                                                   ##STR145##                                                                                         ##STR146##         red                               83                                                                                   ##STR147##                                                                                         ##STR148##         red                               84                                                                                   ##STR149##                                                                                         ##STR150##         red                               85                                                                                   ##STR151##                                                                                         ##STR152##         red                               86                                                                                   ##STR153##                                                                                         ##STR154##         red                               87                                                                                   ##STR155##                                                                                         ##STR156##         red                               88                                                                                   ##STR157##                                                                                         ##STR158##         red                               89                                                                                   ##STR159##                                                                                         ##STR160##         red                               90                                                                                   ##STR161##                                                                                         ##STR162##         red                               91                                                                                   ##STR163##                                                                                         ##STR164##         red                               92                                                                                   ##STR165##                                                                                         ##STR166##         red                               93                                                                                   ##STR167##                                                                                         ##STR168##         red                               94                                                                                   ##STR169##                                                                                         ##STR170##         red                               95                                                                                   ##STR171##                                                                                         ##STR172##         red                               96                                                                                   ##STR173##                                                                                         ##STR174##         red                               97                                                                                   ##STR175##                                                                                         ##STR176##         red                               98                                                                                   ##STR177##                                                                                         ##STR178##         red                               99                                                                                   ##STR179##                                                                                         ##STR180##         red                               100                                                                                  ##STR181##                                                                                         ##STR182##         red                               101                                                                                  ##STR183##                                                                                         ##STR184##         red                               102                                                                                  ##STR185##                                                                                         ##STR186##         red                               __________________________________________________________________________

EXAMPLE 103

6 parts of 5-amino-4-cyano-3-[2-(N-acetyl-N-ethylamino)-ethyl]-isothiazole were introduced into 35 parts of a 3:1 mixture of glacial acetic acid and propionic acid. 15 parts of 85% strength sulfuric acid were added, after which 8 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at 0°-5° C., and stirring was continued for 4 hours at this temperature.

6.6 parts of N-ethyl-N-(2-propylaminocarbonyloxy)ethyl-m-toluidine were suspended in 10 parts by volume of 30% strength hydrochloric acid, 0.3 part of a fatty alcohol oxyethylate and 120 parts of water. 130 parts of ice were added, after which the diazonium salt solution was run in. When coupling was complete, the resulting dye suspension was filtered, and the filter cake was washed neutral with water and dried at 50° C. under reduced pressure to give 8 parts of the dye of the formula ##STR187## This dye dyes polyesters in clear violet hues.

    __________________________________________________________________________     DNNK                                                                           Ex-                                          Hue on                            ample                                                                              Diazo component    Coupling component    polyesters                        __________________________________________________________________________     104                                                                                 ##STR188##                                                                                        ##STR189##           red                               105 "                                                                                                  ##STR190##           red                               106 "                                                                                                  ##STR191##           red                               107 "                                                                                                  ##STR192##           red                               108 "                                                                                                  ##STR193##           red                               109 "                                                                                                  ##STR194##           red                               110 "                                                                                                  ##STR195##           red                               111 "                                                                                                  ##STR196##           red                               112 "                                                                                                  ##STR197##           red                               113 "                                                                                                  ##STR198##           red                               114 "                                                                                                  ##STR199##           violet                            115                                                                                 ##STR200##                                                                                        ##STR201##           red                               116 "                                                                                                  ##STR202##           violet                            117                                                                                 ##STR203##                                                                                        ##STR204##           red                               118 "                                                                                                  ##STR205##           red                               119 "                                                                                                  ##STR206##           red                               120 "                                                                                                  ##STR207##           red                               121                                                                                 ##STR208##                                                                                        ##STR209##           blue                              122 "                                                                                                  ##STR210##           red                               123 "                                                                                                  ##STR211##           red                               124 "                                                                                                  ##STR212##           red                               __________________________________________________________________________ 

We claim:
 1. A compound of the formula: ##STR213## where R is hydrogen, C₁ -C₄ -alkyl, phenyl, chlorophenyl, methylphenyl, methoxyphenyl or nitrophenyl; R¹ is allyl, C₁ -C₈ -alkyl, C₁ -C₈ -alkyl substituted by C₁ -C₈ -alkoxy, phenoxy, phenyl or C₁ -C₈ -alkanoyloxy, cyclopentyl, cyclohexyl, and methylcyclohexyl, norbornyl, phenyl or phenyl substituted by chlorine, methyl or alkoxy; R² is C₁ -C₁₀ -alkanoyl, C₁ -C₁₀ -alkanoyl substituted by alkoxy or phenoxy, cyclohexanoyl, benzoyl, benzoyl substituted by chlorine, methyl or methoxy, C₁ -C₈ -alkoxycarbonyl, aminocarbonyl, phenylaminocarbonyl, CH₃ NHCO, C₂ H₅ NHCO, C₃ H₇ NHCO, C₄ H₉ NHCO, (CH₃)₂ NCO, CH₃ SO₂, C₆ H₅ SO₂ or p--CH₃ --C₃ H₄ --SO₂ ; or R¹ and R², together with the nitrogen atom, form a ring system selected from the group consisting of: ##STR214## and K is a radical of a coupling component.
 2. The compound as claimed in claim 1, wherein KH is of the formula: ##STR215## where R³ is hydrogen, alkyl, aralkyl or aryl, R⁴ is hydrogen or R⁵, where R⁵ is C₁ -C₆ -alkyl, or C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexyl-aminocarbonyloxy, phenylamino-carbonyloxy, C₁ -C₈ -alkoxy-carbonyl, C₁ -C₈ -alkoxyalkoxy-carbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl, or phenyl, benzyl, phenethyl or cyclohexyl, R⁶ and R⁷ are each hydrogen, alkyl, alkoxy, phenoxy, halogen, alkylsulfonylamino, dialkylaminosulfonylamino, benzyloxy, benzylamino or C₁ -C₆ -alkanoylamino, R⁸ is cyano, carbamyl, nitro or carbalkoxy, and R⁹ is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonylmethyl, cyanomethyl, benzyl or phenyl which is monosubstituted or polysubstituted by C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, phenoxy, benzyloxy, phenyl, chlorine, bromine, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -mono- or di-alkylamino, C₁ -C₄ -alkoxyethoxy, C₁ -C₄ -alkyl- or phenyl-mercapto.
 3. The compound as claimed in claim 2, wherein said R⁵ substituent is methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxy-propyl, 2-hydroxy-butyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyl-oxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyl-oxyethyl, 2-ethyl-aminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonyl-ethyl, 2-β-phenyloxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl or 2-phenoxyethoxycarbonylethyl.
 4. A compound of the formula: ##STR216## where R is hydrogen, C₁ -C₄ -alkyl, phenyl, chlorophenyl, methylphenyl, methoxyphenyl or nitrophenyl; R¹ is methyl, ethyl, propyl, butyl, hexyl, octyl, C₂ H₅ -OCH₂ CH₂, CH₃ OCH₂ CH₂ CH₂ --, C₄ H₉ OCH₂ CH₂ CH₂ --, C₆ H₅ OCH₂ CH₂ --, C₆ H₅ OCH₂ CH₂ OCH₂ CH₂ CH₂ --, C₆ H₅ CH₂ -- or C₆ H₅ CH₂ CH₂ --; R² is C₁ -C₁₀ -alkanoyl C₁ -C₁₀ -alkanoyl substituted by alkoxy or phenoxyl, cyclohexanoyl, benzoyl, benzoyl substituted by chlorine, methyl or methoxy, C₁ -C₈ -alkoxycarbonyl, aminocarbonyl, phenylaminocarbonyl, CH₃ NHCO, C₂ H₅ NHCO, C₃ H₇ NHCO, C₄ H₉ NHCO, (CH₃)₂ NCO, CH₃ SO₂, C₆ H₅ SO₂ or p--CH₃ --C₆ H₄ --SO₂ ; or R¹ and R², together with the nitrogen atom, form a ring system selected from the group consisting of: ##STR217## and K is a radical of a coupling component. 